CN105047864A - Preparation method of lithium zirconate-coated ternary layered cathode material of lithium ion battery - Google Patents

Preparation method of lithium zirconate-coated ternary layered cathode material of lithium ion battery Download PDF

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CN105047864A
CN105047864A CN201510312734.8A CN201510312734A CN105047864A CN 105047864 A CN105047864 A CN 105047864A CN 201510312734 A CN201510312734 A CN 201510312734A CN 105047864 A CN105047864 A CN 105047864A
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刘向峰
张继成
胡中波
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University of Chinese Academy of Sciences
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a lithium zirconate-coated ternary layered cathode material of a lithium ion battery, and belongs to the technical field of new energy sources. Coating is realized by a hydrothermal method or a room-temperature stirring method; and the method specifically comprises the following three steps: preparation of an oxalate precursor, preparation of a ZrO2-coated oxalate precursor and preparation of a lithium zirconate-coated ternary layered cathode material. According to the method, the bonding strength between a coating layer Li2ZrO3 or Li4ZrO4 and a ternary cathode material of a main phase can be improved; the coating layer is uniform in thickness; and the rate capability and the cycling stability of the lithium ion battery, especially the rate capability are significantly improved. The method provided by the invention is simple in synthetic process, high in production efficiency and suitable for large-scale production, and has the advantages that the materials required by a reactant are available, nontoxic and low in cost; special protection is not needed in the production process; the reaction condition is easy to control; and the obtained product has the advantages of high yield, good result repeatability and the like.

Description

The preparation method of the ternary layered positive electrode of lithium zirconate coated lithium ion battery
Technical field
The present invention relates to lithium zirconate lithium ion conductor series material and (be mainly Li 2zrO 3and Li 4zrO 4) preparation method of the ternary layered positive electrode of coated lithium ion battery, belong to technical field of new energies.
Background technology
The exhaustion of conventional fossil fuel and the day by day serious of environmental pollution, make the exploitation of new forms of energy extremely urgent.And in the utilization that the integrated use of new forms of energy battery and motorization technical barrier are just embodied in electric automobile power battery and technical barrier.Lithium ion battery is considered to one of the most promising energy storage system that can realize electrokinetic cell, but the current energy density of lithium ion battery and the aspect such as power density and fail safe also cannot meet the development need of electric automobile.Positive electrode, as the performance uniquely providing the great limiting lithium ion cell of the material of lithium ion in lithium ion battery, therefore develops the positive electrode with the safety of high-energy-density and high power density very important.The advantages such as theoretical capacity is high because having for ternary layered positive electrode, cyclical stability better, cost is lower, toxicity is lower are considered to one of positive electrode of lithium ion battery most potentiality of future generation.But the cyclical stability of ternary layered positive electrode is good not, high rate performance is poor, these factors constrain its extensive use on electric automobile.The main method of the ternary layered positive electrode performance of current improvement has Surface coating (that is: at its Surface coating one deck oxide or other inert material), element doping (as metallic elements such as Al, Ru).These methods can improve cyclical stability and high rate performance (fast charging and discharging performance) to a certain extent, but are also not enough to the requirement meeting electric automobile, therefore develop more effective method of modifying very important.Lithium zirconate inorganic lithium ion conductor series material (is mainly Li 2zrO 3and Li 4zrO 4) be that a class thermal stability is fabulous and have higher lithium ion transport performance, if be coated on positive electrode surface, not only can prevent the decomposition reaction that electrolyte causes with direct contact of positive electrode surface, also will be conducive to the transmission of lithium ion, thus greatly improve the cyclical stability, particularly high rate performance of lithium ion battery.Although have research by " rear coated " method by Li 2zrO 3be coated on positive electrode surface, these methods all need first to prepare positive electrode, and then by Li 2zrO 3be coated on positive electrode surface.But material prepared by this " rear coated " method, the adhesion between coating layer and principal phase is often poor, and coating thickness is also uneven, thus affects chemical property, particularly high rate capability.
Summary of the invention
The present invention proposes the new method of one " synchronous lithiumation " legal system for lithium zirconate coated lithium ion battery tertiary cathode material, i.e. lithium zirconate coating layer Li 2zrO 3or Li 4zrO 4formed in lithiation process with principal phase tertiary cathode material, the method can improve Li simultaneously 2zrO 3or Li 4zrO 4and the bond strength between principal phase tertiary cathode material, and coating thickness is even, and the high rate performance of lithium ion battery and cyclical stability obtain and significantly improve, especially high rate performance.
The preparation method of the ternary layered positive electrode of a kind of lithium zirconate coated lithium ion battery that the present invention proposes, is characterized in that adopting hydro thermal method coated, specifically comprises the following steps:
(1) preparation of oxalate precursor:
According to x:y:(1-x-y) mol ratio by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, wherein x≤0.8, y≤0.4, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor, then configures the H that molar concentration is 1mol/L 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution joins in metallic ion mixed liquor, produces sediment, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 80 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni xco ymn 1-x-yc 2o 42H 2o (x≤0.8, y≤0.4);
(2) ZrO 2the preparation of coated oxalate precursor:
The oxalate precursor 500mg that step (1) obtains is dispersed in 10mL absolute ethyl alcohol, stir and ultrasonic disperse 10 minutes, according to Zr:(Ni+Co+Mn)=the molar ratio of α: 100, add the Zr (OC that mass percent concentration is 10%wt 4h 9) 4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, hydrothermal treatment consists 5 ~ 12 hours at 150 ~ 180 DEG C, naturally after cooling, centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) preparation of the coated ternary layered positive electrode of lithium zirconate:
According to Li:(Ni+Co+Mn)=(105+2 α)/100 or Li:(Ni+Co+Mn) molar ratio of=(105+4 α)/100, wherein 1≤α≤15, the oxalate precursor that step (2) is prepared and LiOHH 2o grinds and mixes, and is placed in Muffle furnace, and with the heating rate of 3 ~ 5 DEG C/min, at 700 ~ 1000 DEG C, calcination processing 12 ~ 24 hours, naturally cools to room temperature, obtain Li 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
The preparation method of the ternary layered positive electrode of a kind of lithium zirconate coated lithium ion battery that the present invention proposes, is characterized in that adopting direct paddling process coated, specifically comprises the following steps:
(1) preparation of oxalate precursor:
According to x:y:(1-x-y) mol ratio by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, wherein x≤0.8, y≤0.4, the molar concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor, then configures the H that molar concentration is 1mol/L 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution joins in metallic ion mixed liquor, produces sediment, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 80 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni xco ymn 1-x-yc 2o 42H 2o (x≤0.8, y≤0.4);
(2) ZrO 2the preparation of coated oxalate precursor:
The oxalate precursor 2g that step (1) obtains is dispersed in 25mL absolute ethyl alcohol, add and to stir after 10 μ L ~ 1mL ammoniacal liquor and ultrasonic disperse 10 minutes, according to Zr:(Ni+Co+Mn)=the molar ratio of α: 100, add the Zr (OC that mass percent concentration is 10%wt 4h 9) 4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is stirred 24 ~ 72 hours under 300-700 rotating speed at 25 ~ 75 DEG C, the completely rear centrifuge washing of question response, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) preparation of the coated ternary layered positive electrode of lithium zirconate:
According to Li:(Ni+Co+Mn)=(105+2 α)/100 or Li:(Ni+Co+Mn) molar ratio of=(105+4 α)/100, wherein 1≤α≤15, the oxalate precursor that step (2) is prepared and LiOHH 2o grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3 ~ 5 DEG C/min, processes 12 ~ 24 hours, naturally cool to room temperature, obtain Li at 700 ~ 1000 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated coated lithium ion battery.
Technical characterstic of the present invention and beneficial effect:
The preparation method that the present invention proposes is the in-situ preparation method of " synchronous lithiumation ", i.e. coating layer Li 2zrO 3formed in lithiation process with the ternary layered positive electrode of principal phase simultaneously, and by feed change ratio, also successfully by Li 4zrO 4be coated on tertiary cathode material surface, this is also first by Li 4zrO 4for the surface modification of positive electrode.
Preparation method's advantage of the present invention is: prepared lithium zirconate inorganic lithium ion conductor series material by simple co-precipitation, synchronous lithiumation and high temperature solid-phase sintering reaction and (be mainly Li 2zrO 3and Li 4zrO 4) evenly coated ternary layered positive electrode.
The inventive method synthesis technique is simple, and production efficiency is high, suitability for scale production.And the inventive method raw material had required for reactant is easy to get, nontoxic, with low cost, production process is without the need to special protection, and easy control of reaction conditions, the product obtained has the advantages such as output is large, result is reproducible.
Lithium zirconate inorganic lithium ion conductor series material prepared by the inventive method (is mainly Li 2zrO 3and Li 4zrO 4) coated ternary layered positive electrode, compared with existing not coated material, be all greatly improved in the battery performances such as circulating battery stability and multiplying power and improve.
Accompanying drawing explanation
Fig. 1 (a), (b) are respectively Li prepared by the inventive method 2zrO 3and Li 4zrO 4the X-ray diffractogram of coated ternary layered positive electrode.
Fig. 2 (a), (b) are respectively coated Li 2zrO 3and Li 4zrO 4with not coated Li 2zrO 3and Li 4zrO 4the specific discharge capacity circulation comparison diagram of ternary layered positive electrode under 5C (1000mA/g) current density.
Fig. 3 (a), (b) are respectively coated Li 2zrO 3and Li 4zrO 4with not coated Li 2zrO 3and Li 4zrO 4the specific discharge capacity circulation comparison diagram of ternary layered positive electrode under different multiplying.
Introduce the embodiment of the inventive method below:
Embodiment one:
(1) according to the mol ratio of 1:1:1 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 500mg obtained above and be dispersed in 10mL absolute ethyl alcohol, stirs and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=3:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 180 DEG C, process 5 hours, naturally after cooling, centrifuge washing 80 DEG C of dryings.
(3) the coated LiNi of lithium zirconate 0.333co 0.333mn 0.333o 2preparation: according to the mol ratio of 100:111 or 100:117 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 800 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Gained Li 2zrO 3coated ternary layered positive electrode characterizes: gained Li 2zrO 3coated ternary layered positive electrode through X-ray diffractometer analysis can be pure phase, as shown in Figure 1a.To Li under the discharge current density of 5C (1000mA/g) 2zrO 3coated ternary material carries out battery performance test, and charge and discharge cycles 400 is enclosed, and contrasts, as shown in Figure 2 a with not coated ternary material.Test battery high rate performance under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C discharge current density, result as shown in Figure 3 a.
Gained Li 4zrO 4coated ternary layered positive electrode characterizes: gained Li 4zrO 4coated ternary layered positive electrode through X-ray diffractometer analysis can be pure phase, as shown in Figure 1 b.To Li under the discharge current density of 5C (1000mA/g) 4zrO 4coated ternary material carries out battery performance test, and charge and discharge cycles 400 is enclosed, and contrasts, as shown in Figure 2 b with not coated ternary material.Test battery high rate performance under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C discharge current density, result as shown in Figure 3 b.
Embodiment two:
(1) according to the mol ratio of 4:3:3 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 2g obtained above be dispersed in 25mL absolute ethyl alcohol add 50 μ L ammoniacal liquor stir and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=3:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then this mixed liquor is stirred 24 hours under 300 rotating speeds at 25 DEG C, question response completely after centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) the coated LiNi of lithium zirconate 0.4co 0.3mn 0.3o 2preparation: according to the mol ratio of 100:111 or 100:117 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 800 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment three:
(1) according to the mol ratio of 5:3:2 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 degree of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 500mg obtained above and be dispersed in 10mL absolute ethyl alcohol, stirs and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=5:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, under 180 degrees Celsius, process 5 hours, naturally after cooling, centrifuge washing 80 DEG C of dryings.
(3) the coated LiNi of lithium zirconate 0.5co 0.3mn 0.2o 2preparation: according to the mol ratio of 100:115 or 100:125 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 850 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment four:
(1) according to the mol ratio of 8:1:1 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 2g obtained above be dispersed in 25mL absolute ethyl alcohol add 100 μ L ammoniacal liquor stir and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=5:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then this mixed liquor is stirred 24 hours under 300 rotating speeds at 50 DEG C, question response completely after centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) the coated LiNi of lithium zirconate 0.8co 0.1mn 0.1o 2preparation: according to the mol ratio of 100:115 or 100:125 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 850 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment five:
(1) according to the mol ratio of 1:1:1 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 500mg obtained above and be dispersed in 10mL absolute ethyl alcohol, stirs and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=1:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 180 DEG C, process 5 hours, naturally after cooling, centrifuge washing 80 degree of dryings.
(3) the coated LiNi of lithium zirconate 0.333co 0.333mn 0.333o 2preparation: according to the mol ratio of 100:107 or 100:109 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 800 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment six:
(1) according to the mol ratio of 4:3:3 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 2g obtained above be dispersed in 25mL absolute ethyl alcohol add 0.5mL ammoniacal liquor stir and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=10:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then this mixed liquor is stirred 24 hours under 300 rotating speeds at 75 DEG C, question response completely after centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) the coated LiNi of lithium zirconate 0.4co 0.3mn 0.3o 2preparation: according to the mol ratio of 100:107 or 100:109 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 800 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment seven:
(1) according to the mol ratio of 5:3:2 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 500mg obtained above and be dispersed in 10mL absolute ethyl alcohol, stirs and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=10:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, at 180 DEG C, process 5 hours, naturally after cooling, centrifuge washing 80 DEG C of dryings.
(3) the coated LiNi of lithium zirconate 0.333co 0.333mn 0.333o 2preparation: according to the mol ratio of 100:125 or 100:145 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 700 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
Embodiment eight:
(1) according to the mol ratio of 8:1:1 by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor.Configure the H of 1mol/L again 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution adds in metallic ion mixed liquor, produces a large amount of precipitation immediately, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol 2 times respectively, is placed in 80 DEG C of baking ovens dryings 12 hours, namely obtains oxalate precursor;
(2) ZrO 2the synthesis of coated oxalate precursor: take oxalate precursor 2g obtained above be dispersed in 25mL absolute ethyl alcohol add 0.7mL ammoniacal liquor stir and ultrasonic disperse.According to Zr:(Ni+Co+Mn) molar ratio of=10:100, add the Zr (OC that concentration is 10%wt 4h 9) 4ethanol solution, dispersed with stirring is even.Then this mixed liquor is stirred 24 hours under 300 rotating speeds at 60 DEG C, question response completely after centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) the coated LiNi of lithium zirconate 0.8co 0.1mn 0.1o 2preparation: according to the mol ratio of 100:125 or 100:145 by the oxalate precursor of above-mentioned preparation and LiOHH 2o is ground, and is placed in Muffle furnace, with the heating rate of 5 DEG C/min, processes 12 hours, can obtain Li after naturally cooling to room temperature at 700 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.

Claims (2)

1. a preparation method for the ternary layered positive electrode of lithium zirconate coated lithium ion battery, is characterized in that, adopts hydro thermal method coated, specifically comprises the following steps:
(1) preparation of oxalate precursor:
According to x:y:(1-x-y) mol ratio by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, wherein x≤0.8, y≤0.4, the total mol concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor, then configures the H that molar concentration is 1mol/L 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution joins in metallic ion mixed liquor, produces sediment, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 80 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni xco ymn 1-x-yc 2o 42H 2o (x≤0.8, y≤0.4);
(2) ZrO 2the preparation of coated oxalate precursor:
The oxalate precursor 500mg that step (1) obtains is dispersed in 10mL absolute ethyl alcohol, stir and ultrasonic disperse 10 minutes, according to Zr:(Ni+Co+Mn)=the molar ratio of α: 100, add the Zr (OC that mass percent concentration is 10%wt 4h 9) 4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is proceeded in the teflon-lined water heating kettle of finish-drying, hydrothermal treatment consists 5 ~ 12 hours at 150 ~ 180 DEG C, naturally after cooling, centrifuge washing, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) preparation of the coated ternary layered positive electrode of lithium zirconate:
According to Li:(Ni+Co+Mn)=(105+2 α)/100 or Li:(Ni+Co+Mn) molar ratio of=(105+4 α)/100, wherein 1≤α≤15, the oxalate precursor that step (2) is prepared and LiOHH 2o grinds and mixes, and is placed in Muffle furnace, and with the heating rate of 3 ~ 5 DEG C/min, at 700 ~ 1000 DEG C, calcination processing 12 ~ 24 hours, naturally cools to room temperature, obtain Li 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated lithium ion battery.
2. a preparation method for the ternary layered positive electrode of lithium zirconate coated lithium ion battery, is characterized in that, adopts direct paddling process coated, specifically comprises the following steps:
(1) preparation of oxalate precursor:
According to x:y:(1-x-y) mol ratio by NiSO 4, CoSO 4, MnSO 4be dissolved in 50mL water, wherein x≤0.8, y≤0.4, the molar concentration making W metal ion, metal Co ion and metal M n ion is 1mol/L, obtains metallic ion mixed liquor, then configures the H that molar concentration is 1mol/L 2c 2o 4solution 50mL, by H under magnetic agitation 2c 2o 4solution joins in metallic ion mixed liquor, produces sediment, stirs after 2 hours, centrifugation, uses deionized water and washes of absolute alcohol sediment 2 times respectively, sediment is placed in 80 DEG C of baking ovens dry 12 hours, obtain oxalate precursor, the molecular formula of oxalate precursor is: Ni xco ymn 1-x-yc 2o 42H 2o (x≤0.8, y≤0.4);
(2) ZrO 2the preparation of coated oxalate precursor:
The oxalate precursor 2g that step (1) obtains is dispersed in 25mL absolute ethyl alcohol, add and to stir after 10 μ L ~ 1mL ammoniacal liquor and ultrasonic disperse 10 minutes, according to Zr:(Ni+Co+Mn)=the molar ratio of α: 100, add the Zr (OC that mass percent concentration is 10%wt 4h 9) 4ethanol solution, wherein 1≤α≤15, dispersed with stirring is even, obtain mixed liquor, then this mixed liquor is stirred 24 ~ 72 hours under 300-700 rotating speed at 25 ~ 75 DEG C, the completely rear centrifuge washing of question response, the sediment obtained by centrifuge washing at 80 DEG C dry 12 hours, obtains ZrO 2coated oxalate precursor;
(3) preparation of the coated ternary layered positive electrode of lithium zirconate:
According to Li:(Ni+Co+Mn)=(105+2 α)/100 or Li:(Ni+Co+Mn) molar ratio of=(105+4 α)/100, wherein 1≤α≤15, the oxalate precursor that step (2) is prepared and LiOHH 2o grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3 ~ 5 DEG C/min, processes 12 ~ 24 hours, naturally cool to room temperature, obtain Li at 700 ~ 1000 DEG C 2zrO 3or Li 4zrO 4the ternary layered positive electrode of coated coated lithium ion battery.
CN201510312734.8A 2015-06-09 2015-06-09 Preparation method of lithium zirconate-coated ternary layered cathode material of lithium ion battery Pending CN105047864A (en)

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CN114551827A (en) * 2022-01-24 2022-05-27 惠州锂威新能源科技有限公司 Negative electrode material, preparation method thereof, negative plate and secondary battery
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CN105789565A (en) * 2016-04-11 2016-07-20 中国科学院大学 Preparing method of zirconic acid lithium cladding lithium-ion battery lithium-rich manganese base layer oxide anode material
CN109461893A (en) * 2017-12-29 2019-03-12 北京当升材料科技股份有限公司 A kind of Olivine-type Cathode Material in Li-ion Batteries and preparation method thereof
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CN114551827A (en) * 2022-01-24 2022-05-27 惠州锂威新能源科技有限公司 Negative electrode material, preparation method thereof, negative plate and secondary battery
CN117276534A (en) * 2023-11-21 2023-12-22 宜宾光原锂电材料有限公司 High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery
CN117276534B (en) * 2023-11-21 2024-02-13 宜宾光原锂电材料有限公司 High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery

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